Brémond, Éric, Savarese, Marika, Pérez-Jiménez, Ángel J., Sancho-Garcia, Juan-Carlos, Adamo, Carlo
Range-Separated Double-Hybrid Functional from Nonempirical Constraints
Journal of Chemical Theory and Computation. 2018, 14(8): 4052-4062. doi:10.1021/acs.jctc.8b00261
URI: http://hdl.handle.net/10045/79212
DOI: 10.1021/acs.jctc.8b00261
ISSN: 1549-9618 (Print)
Abstract: 
On the basis of our previous developments in the field of nonempirical double hybrids, we present here a new exchange-correlation functional based on a range-separated model for the exchange part and integrating a nonlocal perturbative correction to the electron correlation contribution. Named RSX-QIDH, the functional is free from any kind of empirical parametrization. Its range-separation parameter is set to recover the total energy of the hydrogen atom, thus eliminating the self-interaction error for this one-electron system. Subsequent tests on some relevant benchmark data sets confirm that the self-interaction error is particularly low for RSX-QIDH. This new functional provides also correct dissociation profiles for charged rare-gas dimers and very accurate ionization potentials directly from Kohn–Sham orbital energies. Above all, these good results are not obtained at the expense of other properties. Indeed, further tests on standard benchmarks show that RSX-QIDH is competitive with the more empirical ωB97X-2 double hybrid and outperforms the parent LC-PBE long-range corrected hybrid, thus underlining the important role of the nonlocal perturbative correlation.
Keywords:Range-separated model, Double-hybrid functional, Nonempirical constraints
American Chemical Society
info:eu-repo/semantics/article